ISSN 10637745, Crystallography Reports, 2010, Vol. 55, No. 7, pp. 1220–1222. © Pleiades Publishing, Inc., 2010.

STRUCTURE OF ORGANIC
COMPOUNDS

Synthesis and XRay Crystal Structure Determination

of Npmethylphenyl4benzoyl3,4diphenyl2azetidinone1
Mehmet Kabaka, Hülya Şenözb, Ayhan Elmalia, Vildan Adarb, Ingrid Svobodac,
ˆ
Michal Dus ekd, and Karla Fejfarovád
a
Department of Engineering Physics, Faculty of Engineering, University of Ankara, 06100 Tandogan, Ankara, Turkey
email: kabak@eng.ankara.edu.tr
b
Hacettepe University, Faculty of Sciences, Department of Chemistry, 06532, Beytepe Ankara, Turkey
c
Institute of Material Science, Darmstadt University of Technology, Petersenstrasse 23, D64287 Darmstadt, Germany
d
Institute of Physics, Na Slovance 2, 182 21 Praha 8, Czech Republic
Received March 23, 2010

Abstract—The title compound, C29H23NO2, has been characterized by singlecrystal Xray diffraction at two
different temperatures (303 K and 120 K) and wavelengths (MoKα and CuKα). The noncentrosymmetric
hexagonal crystal structure contains fourmembered planar βlactam ring with an unusually long C–C bond.
The βlactam ring is almost planar.
DOI: 10.1134/S1063774510070229

1
INTRODUCTION The structure has been deposited with the Cam
bridge Structural Data Centre (CCDC nos. 777926 (at
The 2azetidinone (βlactam) group is a crucial 120 K) and 778734 (at 303 K)).
structural fragment of a class of important antibiotics
[1]. Antibiotic activity of 2azetidinone ring is corre
lated with shortening of the C=O bond, and lengthen COMMENT
ing of the C–N bond. The reported structure has been
Figure shows the molecule with atom labels and
investigated in the framework of our research on the
with the residues R1 to R5 indicated. Introduction of
influence of substituents on the activity and selectivity the phenyl group to the position R5 causes the
of the monocyclic βlactams [2–5]. increase of the C2–C3 bond length to 1.606(3) Å
(Tables 2 and 3). Although this C–C distance is not
usual, even longer C–C distances have been reported
EXPERIMENTAL
A solution of 0.02 mol of phenylacetyl chloride in
50 ml dry ether was added over 1 h to a solution of
C22 C21
0.01 mol of 2[(4methylphenyl)imino]1,2diphe
nylethanone and 0.02 mol of triethylamine in 100 ml C20
C15 C23 R3
of dry ether at room temperature. The mixture was C14
stirred over 24 h. The amine salt was removed by filtra C13 C19
tion. The filtrate was concentrated on a rotary evapo C16 R2 C18
rator, and the residue was recrystallized from 95% C17
C12 R4
C9
hexane. C11 C3 C8
O2 N1
Crystallographic characteristics, experimental C25 C4 C7
details, and the results of crystal structure refinement C26
C2
C1
R1 C10
for the prepared compound are presented in Table 1. C24
R5 C5 C6
C29
The structure was solved by direct methods. Non C27 O1
hydrogen atoms were refined anisotrophically, and all C28
hydrogen atoms were located geometrically. The iso
tropic atomic displacement parameters of hydrogen
atoms were evaluated as 1.2Ueq of the parent atom. The molecular structure of the titled compound. Displace
1 The article is published in the original.
ment ellipsoids are drawn at the 50% probability level. R1–
R5 are residues.

1220
 SYNTHESIS AND XRAY CRYSTAL STRUCTURE DETERMINATION 1221

Table 1. Crystallographic data of the title structure

C29H23N1O2
Chemical Formula
At 120 K At 303 K
System, sp. gr., Z Hexagonal, P61, 6 Hexagonal, P61, 6
a, Å 10.7303(2) 10.814(1)
c, Å 32.9495(4) 33.291(2)
3
V, Å 3285.51(10) 3371.6(5)
3
Dx, g/cm 1.266 1.234
Radiation, λ, Å CuKα MoKα
μ, mm–1 0.62 0.077
Sample size, mm 0.49 × 0.31 × 0.27 0.50 × 0.32 × 0.22
Diffractometer Gemini, Oxford Diffraction XCALIBUR Oxford Diffraction
Scan mode ω ω
Absorption corrections, Tmin, Tmax CrysAlis, 0.689, 0.842 CrysAlis, 0.9625, 0.9833
θmax, deg 66.98 26.37
Collection range –12 ≤ h ≤ 12, –12 ≤ k ≤ 12, –39 ≤ l ≤ 39 –12 ≤ h ≤ 13, –13 ≤ k ≤ 13, –41 ≤ l ≤ 28
Number of reflections: measured/unique 82427/1987, 0.034/ 1973 (n = 3) 24434/4081, 0.097/2647 (n = 2)
(N1)/with I > nσ(I) (N2)
Refinement method least squares for F2 least squares for F2
Number of refined parameters 289 289
2
Weighting scheme w= 1/(σ2(I) + 0.0016I2) w = 1/[σ2( F o ) + (0.0735P)2 + 0.0000P],
2 2
where P = ( F o + 2 F c )/3
wR2 for N1 0.078 0.1311
R1 for N2 0.025 0.0582
S 1.94 1.010
Δρmax/Δρmin, e/Å3 0.18/–0.15 0.23/–0.17
Program packages:
Data collection CrysAlis CCD [6] CrysAlis CCD [6]
Structure solution SIR2002 [7] SHELXS97 [9]
Structure refinement Jana2006 [8] SHELXL97 [9]

Table 2. Selected bond lengths (Å) and angles (deg) of the title molecule at 120 and 303 K
120 K 303 K 120 K 303 K
O1–C1 1.207(2) 1.221(4) C1–N1–C3 96.0(2) 95.7(2)
O2–C11 1.221(3) 1.202(4) C1–N1–C4 133.2(2) 132.9(2)
N1–C1 1.370(3) 1.356(5) C3–N1–C4 130.6(2) 131.3(2)
N1–C3 1.487(2) 1.480(4) O1–C1–N1 132.4(2) 132.1(3)
N1–C4 1.410(3) 1.419(4) O1–C1–C2 134.6(2) 134.3(3)
C1–C2 1.533(3) 1.513(4) N1–C1–C2 92.9(2) 93.5(3)
C2–C3 1.606(3) 1.598(4) C1–C2–C3 85.2(1) 85.1(2)
C2–C24 1.512(2) 1.518(4) N1–C3–C18 112.1(1) 110.8(3)
C3–C11 1.540(2) 1.537(4) C2–C3–C11 112.2(1) 112.8(2)
C3–C18 1.528(3) 1.521(4) C2–C3–C18 115.3(2) 115.0(2)
C7–C10 1.506(4) 1.518(6) C11–C3–C18 116.6(2) 116.3(3)

CRYSTALLOGRAPHY REPORTS Vol. 55 No. 7 2010

1222 MEHMET KABAK et al.

Table 3. Bond length parameters of 2azetidinones

Ref. R1 R2 R3 R4 R5 N1–C3 C2–C3 C1–C2 N1–C1 C1–O1
[2] Ph H Ph Cl Cl 1.469 1.571 1.543 1.362 1.186
[5] Ph COPh Ph Cl Cl 1.497 1.601 1.526 1.368 1.199
This work Ph–Me COPh Ph H Ph 1.487 1.606 1.533 1.370 1.207

in the literature for the 2azetidinone compounds with
bulky substituents: 1.621 Å in (2,2'bipyridineN,N')
tricarbonyl(3,3,4,4tetraphenylazetidin2oneN)
rhenium tetrahydrofuran solvate [10], and 1.625 Å
in spiro(3,3diphenyl1propylazetidin2one4,1'
2'diphenylacetoxy3'phenylindene) [11].
The longest known single carboncarbon bond
1.72 Å has been found for the compound having
vicinal tetraphenyl substituents in cyclobutane
ring [12–14].
The elongation of C2–C3 bond distance can be
explained by steric repulsion between R3 and R5 phe
2. M. Kabak, Y. Elerman, V. Guner, et al., Acta Crystal
logr. C 55, 1511 (1999).
3. M. Kabak, Y. Elerman, V. Guner, et al., Acta Crystal
logr. C 55, 2115 (1999).
4. M. Kabak, Y. Elerman, V. Guner, and T. N. Durlu, Acta
Crystallogr. C 56, e207 (2000).
5. M. Kabak, V. Guner, Y. Elerman, and T. N. Durlu,
Anal. Sci. 19, 969 (2003).
6. CrysAlis CCD (Oxford Diffraction Ltd, Oxford, UK,
2009).
7. M. C. Burla, M. Camalli, B. Carrozzini, et al., J. Appl.
Cryst. 36, 1103 (2003).

nyl groups [15–17] or by a throughbond interaction
between these trans positioned phenyl groups [18].
Toda et al., [19] found that steric effect is more effec
tive than the other ones.
In this work, the torsion angles between the planes
of 2azetidinone and the R3 and R5 rings are 85.69°
and 76.25°, respectively. The R1 (tolyl) ring attached
to the nitrogen is almost coplanar with the azetidinone
ring because of conjugation of nitrogen lone pair with
the carbonyl group (dihedral angle between R1 and β
lactam plane is 7.23°). As a result, N1–C1 bond is
shorter, 1.370 Å, than expected.
ACKNOWLEDGMENTS
We acknowledge the Grant Praemium Academiae
of the Academy of Sciences the Czech Republic and
the institution research plan AVOZ10100521 of the
Institute of Physics.
V. Adar thanks to Hacettepe University Scientific
Research Council (project no.: 07A601009).
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CRYSTALLOGRAPHY REPORTS Vol. 55 No. 7 2010